EP1725647B1 - Verbesserte saure chemie für säuberung nach cmp - Google Patents

Verbesserte saure chemie für säuberung nach cmp Download PDF

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Publication number
EP1725647B1
EP1725647B1 EP05702325A EP05702325A EP1725647B1 EP 1725647 B1 EP1725647 B1 EP 1725647B1 EP 05702325 A EP05702325 A EP 05702325A EP 05702325 A EP05702325 A EP 05702325A EP 1725647 B1 EP1725647 B1 EP 1725647B1
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Prior art keywords
cleaning
metal
cleaning solution
piece
cmp
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English (en)
French (fr)
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EP1725647A1 (de
Inventor
Matthew L. Fisher
Ashutosh Misra
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
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    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/267—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3272—Urea, guanidine or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes

Definitions

  • a "semiconductor work-piece” is a microelectronic device, which has not completed the fabrication process, typically a silicon wafer with active regions formed in or on the surface of the silicon wafer. Connections to the active regions are made using multiple layers of metal, typically copper and tungsten, which has been deposited on the silicon substrate.
  • a damascene process is used whereby the copper is deposited into lines etched into the inter-layer dielectric and then the excess copper is removed and the surface planarized using a CMP process, followed by a cleaning step.
  • Post-CMP cleaning The goal of the cleaning process is to remove residues left by the CMP step from the semiconductor work-piece surface without significantly etching the metal, leaving deposits on the surface, or imparting significant organic (such as carbon) contamination to the semiconductor work-piece. Furthermore, it is desirable to protect the metal surfaces from corrosion by various mechanisms such as chemical etching, galvanic corrosion or photo-induced corrosion. Corrosion of the metal surfaces results in metal recess and thinning of the metal lines. Acidic cleaning solutions are often quite efficient at removing organic contamination from the wafer surface and complexing residual copper. Thus it is desirable to have a cleaning solution that is effective in the moderate to low pH regime. Acidic chemistries are typically utilized in a brush scrubber or megasonic cleaning unit for Post-CMP cleaning.
  • a cleaning solution may contain various chemicals that perform different functions during the cleaning process.
  • a cleaning solution must contain a "cleaning agent.”
  • a “cleaning agent” is the component of solution that removes residual CMP slurry particles, typically particles of metal, from the surface of the semiconductor work-piece.
  • a cleaning solution may also contain "chelating agents,” “corrosion-inhibiting compounds,” and/or “surface-active agents.”
  • a “chelating agent” helps prevent re-deposition of removed metal onto the semiconductor work-piece by complexing the metal in the cleaning solution.
  • a “corrosion-inhibiting compound” is the component of the cleaning solution that protects the metal surface from attack by mechanisms such as the aggressive nature of the cleaning solution, oxidation, post cleaning corrosion, galvanic attack, or photo-induced attack.
  • a “surface-active agent” is a component of the cleaning solution that modifies the wetting characteristics and prevents watermark formation.
  • the optimum cleaning solution should protect the metal surfaces of the semiconductor device from having a high static etch rate and from oxidation of the metal surfaces by forming a protective film on the surface.
  • the metal surfaces of the semiconductor work-piece are typically copper, and form the conducting paths of the semiconductor wafer. Due to the very small size of features on semiconductor wafers, the metal lines are as thin as possible while still carrying the desired electric current. Any oxidation or corrosion on the surface or recess of the metal causes thinning of the lines (dissolution) and results in poor performance or failure of the semiconductor device. Therefore, it is important to protect the metal surfaces from corrosion by forming a suitable corrosion resistant film on the surface of the metal.
  • Some cleaning solutions available in the art do not provide a film forming agent, and thus suffer from a high static etch rate and/or high RMS value.
  • the cleaning solution's corrosion preventing abilities are quantified by measuring the static etch rate or the surface roughness (quantified by RMS, root mean square, value) of a metal surface that has been cleaned with the subject solution.
  • a high static etch rate indicates dissolution of the metal surface is occurring.
  • a high RMS value indicates a rough surface caused by attack of the metal.
  • An effective protective film reduces the corrosion of the metal as indicated by static etch rate and RMS values after cleaning.
  • the corrosion resistance of a cleaning solution can also be directly measured using electrochemical means known to those skilled in the art. I
  • One preferred method of protecting the metal surface from oxidation corrosion is by passivating the metal surface after or during cleaning. Some existing acidic cleaning chemistries do not passivate the metal, resulting in corrosion during and after the cleaning step by oxidation of the metal surface.
  • Some chemistries for planarizing a wafer surface include a cleaning step followed by an additional step of rinsing with water or an inhibitor solution. Some rinsing agents can leave deposits on the surface of the work-piece, thus contaminating the wafer.
  • Adding a second step is also a drawback due to the fact that it lengthens the manufacturing process, complicates the process by having to handle more chemicals and more steps, and provides one more possible source of contamination or other quality control problems.
  • a process that cleans and protects the surface of the semiconductor work-piece is desirable.
  • the ability of the cleaning chemistry to remove residual metals and retain them in the cleaning solution is also an important characteristic of a Post-CMP cleaning solution.
  • Chemicals that can complex the residual metals in the cleaning solution are effective cleaning solutions because the residual metals are not redeposited on the semiconductor work-piece after they are removed. These complexing chemicals are referred to as "chelating agents.”
  • Cleaning solutions using chemistry that cannot complex the residual metals typically perform poorly at the desired cleaning task. Thus, it is desirable to have a cleaning solution capable of removing and complexing the dissolved metal in the cleaning solution.
  • a surface wetting agent in the cleaning solution.
  • Surface wetting agents prevent contamination of the semiconductor work-piece by helping to stop spotting of the surface caused by droplets clinging to the surface.
  • Spotting also called watermarks
  • on the surface can saturate metrology tools that measure light point defects, thus masking defects in the semiconductor work-piece.
  • the available cleaning solutions do not adequately meet all of the requirements of post-CMP cleaning.
  • the chemistry of the current invention makes use of multiple additives to provide a solution that is not sensitive to oxygen, removes particles efficiently, removes metal from the dielectric surface, is in the neutral to low pH range, protects the metal from corrosion and dissolution, and does not contaminate the semi conductor surface.
  • EP A 1363321 discloses a post CMP washing solution which does not contain corrosion-inhibiting compounds.
  • EP A 1310989 discloses a detergent composition having a pH above neutral.
  • US B 6465403 discloses an aqueous alkaline cleaning composition.
  • US B 6486108 discloses an aqueous cleaning solution for semiconductor processing consisting of a mixture of phosphoric acid and ascorbic acid.
  • US B 6200947 discloses a cleaning solution for semiconductor devices comprising a mixture of 2-mercaptoethanol or thioglycerol and a solution of an alkaline compound.
  • US A 2003/099908 discloses a photoresist stripping mixture solution comprising a carboxyl group containing an acidic compound and an amine or hydroxide.
  • US B 6245208 discloses an electroplating solution for Au-Sn alloys deposition.
  • US A 2003/0171239 discloses a foam composition for cleaning a substrate, comprising at least a fluoride compound and a solvent.
  • the current invention provides a solution for cleaning a semiconductor work-piece that is not sensitive to oxygen, removes residual particles efficiently, removes metal, particularly copper, from the dielectric surface, is in the neutral to low pH range, protects the metal from oxidation, corrosion and dissolution, and does not contaminate the semiconductor surface. Furthermore, cleaning and protecting the metal surfaces are completed in a single step with a single solution.
  • the cleaning solution of the current invention comprises ammonium citrate as a cleaning agent; and ascorbic acid and/or cysteine as a corrosion-inhibiting compound.
  • the cleaning agent of the current invention is also a chelating agent.
  • the cleaning action of the current invention efficiently removes residual particles from the surface of the semiconductor work-piece and also complexes the metal that is removed in solution. Thus the cleaning efficiency is improved by presenting metal from re-depositing on the semiconductor work-piece surface.
  • the corrosion-inhibiting compound of the current invention protects the metal of the semiconductor work-piece from oxidation, and corrosion.
  • the corrosion-inhibiting compound is effective at forming a film on the metal of the semiconductor work-piece that protects metal surfaces from chemical, galvanic and photo-induced attack during and after the cleaning step.
  • One preferred embodiment forms a protective film by reducing the surface of the metal. By protecting the metal surface from attack, the metal retains its desired thickness and electrical carrying capacity.
  • the cleaning solution of the current invention is not highly sensitive to oxygen because it does not contain any oxygen sensitive compounds. Because the cleaning solution is not highly sensitive to oxygen, the performance of the cleaning solution is not affected by the presence of air in the cleaning equipment. Thus, the cleaning solution of the current invention can be used without extra precautions to purge the storage, transfer and cleaning equipment of essentially all air.
  • the cleaning solution of the current invention cleans the semiconductor work-piece and forms a corrosion-inhibiting film on the metal surfaces in the same step. Because the cleaning and corrosion-inhibiting is accomplished in a single step, there is less likelihood of accidental contamination by handling a completely separate solution. Furthermore, valuable processing time is saved by not having to add an additional inhibiting step.
  • Some preferred embodiments of the cleaning solution include a surface-active agent, also referred to as a surface-wetting agent.
  • the surface-active agent helps prevent spotting (watermarks) on the surface that can be a source of contamination or hide defects in the semiconductor work-piece.
  • the present invention is a cleaning solution for cleaning a semiconductor work-piece.
  • the composition of the cleaning solution comprises ammonium citrate as a cleaning agent; and ascorbic acid and/or cysteine as a corrosion-inhibiting compound.
  • the cleaning solution of the invention comprises ammonium citrate, the cleaning agent, and a mixture of ascorbic acid and cysteine, the corrosion inhibiting agents.
  • a preferred mixture has concentrations of 5 wt.% ammonium citrate, 0.5 wt. % ascorbic acid and 0.5 wt. % cysteine.
  • the preferred embodiment can be diluted 5X to 20X with de-ionized (DI) water prior to use.
  • Preferred embodiments of a cleaning solution of the current invention have a neutral to acidic pH. Even more preferred is a pH of about 2 to about 6.
  • the cleaning solution may be supplied in concentrated form, or diluted with water or other suitable diluents known to one skilled in the art.
  • One preferred cleaning solution includes a surface-active agent to promote even wetting of the semiconductor surface.
  • Preferred embodiments include, but are not limited to, non-ionic, anionic, cationic, zwitterionic or amphoteric surfactants or mixtures thereof.
  • Table 1 SP1 particle removal data for Cu wafers exposed to silica particle slurries and cleaned with DI water, a commercially available product and a preferred embodiment of the present invention.
  • All means the total of all defects.
  • Lpd means light point defects.
  • [#] means number. Defect Totals Cleaning Chemistry All Lpd [#] [#] Control Wafer 742 706 DI Water Clean 65431 65402
  • Table 2 Copper and barrier dissolution numbers for patterned wafers exposed to a commercially available product and a preferred embodiment of the present invention.
  • the preferred embodiment is capable of protecting the barrier material from galvanic corrosion.
  • the composition may be practiced in a process other than post-CMP cleaning.
  • the cleaning of semiconductor work-pieces can be accomplished at a variety of concentrations of cleaning solution, temperature and conditions.
  • the invention may be used to clean a variety of surfaces, including but not limited to surfaces containing copper, silicon, and dielectric films.

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  • Chemical & Material Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Claims (13)

  1. Zusammensetzung zum Reinigen eines Halbleiterwerkstücks, enthaltend:
    Ammoniumcitrat, das Reinigungsmittel, und eine Mischung von Ascorbinsäure und Cystein, den korrosionsinhibierenden Mitteln.
  2. Zusammensetzung nach Anspruch 1, die ferner ein Tensid enthält.
  3. Zusammensetzung nach Anspruch 2, wobei das Tensid aus der Gruppe bestehend aus nichtionischen, anionischen, kationischen, zwitterionischen und amphoteren Tensiden und Mischungen davon ausgewählt ist.
  4. Zusammensetzung nach Anspruch 1, die ferner ein Verdünnungsmittel enthält.
  5. Zusammensetzung nach Anspruch 1, wobei der pH-Wert zwischen 2 und 6 liegt.
  6. Verfahren zum Reinigen eines Halbleiterwerkstücks nach der chemisch-mechanischen Planarisierung (CMP) des Wafers bei der Fertigung von Halbleitervorrichtungen, bei dem man:
    ein Halbleiterwerkstück bereitstellt und das Halbleiterwerkstück mit einer Reinigungslösung in Kontakt bringt, enthaltend:
    Ammoniumcitrat, das Reinigungsmittel, und eine Mischung von Ascorbinsäure und Cystein, den korrosionsinhibierenden Mitteln.
  7. Verfahren nach Anspruch 6, bei dem die Reinigungslösung ferner ein Tensid enthält.
  8. Verfahren nach Anspruch 6, bei dem die Reinigungslösung ferner ein Tensid aus der Gruppe bestehend aus nichtionischen, anionischen, kationischen, zwitterionischen und amphoteren Tensiden und Mischungen davon enthält.
  9. Verfahren nach Anspruch 6, bei dem die Reinigungslösung ferner ein Verdünnungsmittel enthält.
  10. Verfahren nach Anspruch 6, bei dem das Halbleiterwerkstück eine Metalleitung, ein Sperrmaterial und ein Dielektrikum aufweist.
  11. Verfahren nach Anspruch 10, bei dem die Metalleitung Kupfer umfaßt.
  12. Verfahren nach Anspruch 11, bei dem das Sperrmaterial Materialien aus der Gruppe bestehend aus Ta, TaN, Ti, TiN, W und WN umfaßt.
  13. Verfahren nach Anspruch 6, bei dem die Reinigungslösung einen pH-Wert zwischen 2 und 6 aufweist.
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US10/956,272 US7087564B2 (en) 2004-03-05 2004-10-01 Acidic chemistry for post-CMP cleaning
PCT/IB2005/000165 WO2005093031A1 (en) 2004-03-05 2005-01-24 Improved acidic chemistry for post-cmp cleaning

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US20080125341A1 (en) 2008-05-29
TWI364455B (en) 2012-05-21
KR20070003854A (ko) 2007-01-05
WO2005093031A1 (en) 2005-10-06
ATE429480T1 (de) 2009-05-15
US20060234888A1 (en) 2006-10-19
US7087564B2 (en) 2006-08-08
US7297670B2 (en) 2007-11-20
CN1914309A (zh) 2007-02-14
JP2007526647A (ja) 2007-09-13
EP1725647A1 (de) 2006-11-29
CN1914309B (zh) 2011-03-23
KR101140970B1 (ko) 2012-05-23
US20050197266A1 (en) 2005-09-08
DE602005014094D1 (de) 2009-06-04
TW200530394A (en) 2005-09-16

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